CN116454221A - Zinc-based composite powder material and preparation method and application thereof - Google Patents
Zinc-based composite powder material and preparation method and application thereof Download PDFInfo
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- CN116454221A CN116454221A CN202211641851.5A CN202211641851A CN116454221A CN 116454221 A CN116454221 A CN 116454221A CN 202211641851 A CN202211641851 A CN 202211641851A CN 116454221 A CN116454221 A CN 116454221A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000011701 zinc Substances 0.000 title claims abstract description 107
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000006073 displacement reaction Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a zinc-based composite powder material, a preparation method and application thereof, wherein the preparation method comprises the steps of mixing zinc powder with Cu 2+ The aqueous solution of (C) is contacted to perform displacement reaction, solid-liquid separation is carried out, and the obtained solid is washed to remove Zn on the surface 2+ And drying to obtain the zinc-based composite powder material. The invention has mild synthesis condition, simple operation and low cost, and can be used for batch or industrialized production; the high work function sphere frame type conductive shell layer can induce uniform deposition of zinc ions at the electrode interface, and can improve structural corrosion of the zinc powder cathode surface, thus obtaining the zinc ion batteryHas excellent cycle stability and rate capability of 1mA/cm ‑2 ，1 mAh/cm ‑2 Can stabilize the cycle 1600 h.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a zinc-based composite powder material, a preparation method and application thereof.
Background
Currently, intelligent wearable devices and integrated electronic products are developing toward miniaturization and light weight. Since the advent of lithium ion batteries, the lithium ion batteries have been widely applied to various portable equipment, electric automobiles and other fields, but at present, the global lithium resources are short, and the problems of inflammability and explosiveness of organic electrolyte, harsh assembly conditions and the like limit the further application of the lithium ion batteries in large-scale energy storage systems.
Aqueous zinc ion batteries have become excellent candidates for next generation large-scale energy storage systems in recent years due to their low cost, high energy density, inherent safety, and environmental friendliness, and have been widely studied. However, several key scientific issues surrounding zinc metal anodes still prevent the large-scale application of zinc ion batteries. For example: during discharge, zn 2+ Resulting in the formation of zinc dendrites that eventually pierce the separator, resulting in a short circuit of the cell; the self-corrosion and hydrogen evolution reaction of the surface of the zinc plate can form inert byproducts (basic zinc sulfate and the like) on the surface of the zinc cathode, so that the surface of the zinc cathode is passivated, and the coulomb efficiency is reduced.
In recent years, researchers have proposed a series of optimization strategies for zinc cathodes, including structural design of zinc cathodes, optimization of electrolyte-cathode interfaces, and the like. However, most of the optimization methods are complicated to operate and severe in conditions, and the two-dimensional zinc plates used as working electrodes and current collectors simultaneously cause a plurality of problems such as depth of discharge, low energy density and irrecoverability.
For example, application publication No.: the invention discloses a zinc metal protective layer material, a preparation method and application thereof, and a Chinese patent of CN113005435A, application publication date 2021 and month 06 and 22, wherein the zinc metal protective layer material is obtained by placing a zinc plate in a metal ion solution and performing displacement reaction, and can provide more active sites, adjust electric field distribution on the surface of an electrode and inhibit dendrite growth, so that the zinc negative electrode has low nucleation overpotential, low polarization voltage, high cycle stability and coulombic efficiency, high zinc reversibility can be realized, and the zinc negative electrode of a water-based zinc ion battery can be modified. However, this invention has the following drawbacks: (1) The manufacturing cost of the zinc plate is too high, which is not beneficial to the industrialization of the industrial scale; (2) The cathode of the whole zinc plate does not completely participate in the reaction and is exhausted, but dendrites in a certain area continuously grow and severely corrode to finally short-circuit, so that the utilization rate of the whole zinc plate is low; and the whole zinc plate is not recycled, so that the resource utilization rate is low, and the production cost of enterprises is increased.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a preparation method of a zinc-based composite powder material, which is simple to operate, short in synthesis period and easy to industrialize.
The invention also provides a zinc-based composite powder material prepared by the method, which has a high work function-based spherical frame type conductive shell layer, can induce uniform deposition of zinc ions at an electrode interface, and can improve structural corrosion of the surface of a zinc powder negative electrode.
The invention also provides application of the zinc-based composite powder material as a negative electrode material in a zinc ion battery.
To achieve the above and other related objects, the present invention provides a method for preparing a zinc-based composite powder material, comprising mixing zinc powder with Cu 2+ The aqueous solution of (C) is contacted to perform displacement reaction, solid-liquid separation is carried out, and the obtained solid is washed to remove Zn on the surface 2+ And drying to obtain the zinc-based composite powder material.
The application uses spherical Cu with high work function through substitution reaction 2 O substance uniformly grows on the surface of zinc powder, and Cu is coated on the surface of zinc powder 2 O and removing Zn precipitated on the surface by washing 2+ Avoiding generating basic zinc salt, and preparing Zn@Cu composite powder material 2 O. The reaction solvent of the method must adopt water, so that other impurity ions are avoided being introduced, and if other organic solvents such as ethanol are adopted, the product cuprous oxide and the ethanol can undergo side reaction to generate impurity products such as acetaldehyde, and the washing effect is poor.
The reaction process of the present application is inferred as follows:
Zn + Cu 2+ → Cu + Zn 2+ (1)
Cu + O 2 → Cu 2 O (2)。
preferably, the zinc powder has a particle size of 500nm to 50. Mu.m, such as 500nm to 800nm,800nm to 1.5. Mu.m, 1.5 μm to 20. Mu.m, 20 μm to 50. Mu.m.
Preferably, the Cu-containing alloy contains 2+ Cu in aqueous solution of (C) 2+ The concentration of (C) is 0.03-1 g/L, such as 0.03-0.05 g/L, 0.05-0.1 g/L, 0.1-1 g/L. Cu (Cu) 2+ Too low a concentration may result in prolonged reaction periods and uneven reaction products, and too high a concentration may result in too severe a reaction to be easily controlled.
More preferably, the Cu-containing alloy contains 2+ Is selected from one or more of copper sulfate aqueous solution, copper chloride aqueous solution and copper acetate aqueous solution.
Preferably, the zinc powder contains Cu 2+ The mass volume ratio of the aqueous solution of (a) is 0.3-0.6 g/mL, such as 0.3-0.4 g/mL, 0.4-0.5 g/mL, 0.5-0.6 g/mL.
Preferably, the displacement reaction is carried out under stirring, the temperature of the displacement reaction being 20 to 30 ℃, such as in particular 20 to 25 ℃,25 to 30 ℃, for 60 to 600 seconds, such as in particular 60 to 120 seconds, 120 to 360 seconds, 360 to 600 seconds.
Preferably, the solid-liquid separation and washing are carried out by adopting a centrifugal separation method, and water is adopted as a washing solvent. The method has high washing strength, and can effectively remove Zn on the surface of the material 2+ Avoiding the generation of basic zinc salt impurities.
Preferably, the centrifugal speed is 6000-8000 r/min, the single centrifugal time is 3-10 min, and the washing times are 3-5 times; the drying temperature is 50-65 ℃ and the drying time is 6-12 h. The washing strength under the washing condition is high, and Zn on the surface of the material can be removed efficiently 2+ Avoiding the generation of basic zinc salt impurities.
The invention also provides the zinc-based composite powder material prepared by the preparation method.
Preferably, the zinc-based composite powder material is prepared by coating Cu on the surface of zinc powder 2 O-ball frame type conductive shell layer, wherein the zinc-based composite powder material is Zn@Cu 2 O。
The invention also provides application of the zinc-based composite powder material as a negative electrode active material in a water-based zinc ion battery. The zinc-based composite powder material prepared by the invention is used as a negative electrode material, and spherical Cu with high work function is used as a negative electrode material 2 O material grows on the surface of zinc powder uniformly, and the higher the work function is, the stronger the electron attraction capability is, so that in the discharge stage, the spherical frame type conductive shell layer with higher work function can induce Zn 2+ Thereby inhibiting dendrite growth, and slowing down structural corrosion of zinc powder, so that the water-based zinc ion battery has excellent cycle stability and rate capability. The successful preparation of the zinc powder cathode is expected to play an important role in a water-based zinc ion battery, and has a large-scale application prospect.
The invention also provides a preparation method of the flexible negative electrode containing the zinc-based composite powder material, which comprises the following steps: .
Uniformly mixing a zinc-based composite powder material, conductive carbon black, PVDF suspension and N-methylpyrrolidone to obtain a flexible anode material; and rolling the flexible negative electrode material on a copper mesh current collector, and drying to obtain the flexible negative electrode. In the technical scheme of the application, the obtained flexible anode material is an elastomer, and the copper mesh is used as a current collector to have bendable flexible performance.
Preferably, the drying temperature is 55 to 65 ℃.
Preferably, the PVDF suspension is 50-60% by mass; the mass volume ratio of zinc powder to PVDF suspension is 8-10 g/mL, and the mass volume ratio of zinc powder to N-methyl pyrrolidone is 8-10 g/mL.
The invention also provides a water-based zinc ion battery with the flexible negative electrode prepared by the preparation method.
As described above, the present invention has the following advantageous effects:
(1) The synthesis condition is mild, the operation is simple, the cost is low, and the batch or industrialized production can be realized;
(2) The high work function sphere frame type conductive shell layer can induce uniform deposition of zinc ions at the electrode interface and improve structural corrosion of the zinc powder cathode surface.
(3) The zinc-based composite powder material is used as a negative electrode material to be applied to a zinc ion battery, and the obtained zinc ion battery has excellent cycle stability and rate capability and is 1mA/cm -2 ，1mAh/cm -2 Can be stably recycled for 1600 hours (about 20 times of the common commercial zinc powder cathode).
Drawings
Fig. 1 shows an SEM image of commercial zinc powder.
FIG. 2 shows the Zn@Cu powder material obtained in example 1 2 SEM image of O.
FIG. 3 shows the Zn@Cu powder material obtained in example 1 2 A TEM image and an HRTEM image of O.
FIG. 4 shows the Zn@Cu powder material obtained in example 1 2 XRD spectrum of O: a is a full spectrum of 5-80 degrees, and B is a partial enlarged view in A.
FIG. 5 shows the Zn@Cu powder material obtained in example 1 2 O surface high resolution XPS energy spectrum.
FIG. 6 shows that the symmetric zinc ion cells prepared in comparative example 1 and example 1 were at 1.0mA/cm -2 And 1.0mAh/cm -2 Long cycle performance.
FIG. 7 shows a commercial zinc powder of comparative example 1 and a Zn@Cu zinc-based composite powder material obtained in example 1 2 When O surfaces are the sameTopography after the interval.
FIG. 8 Zn@Cu of the zinc-based composite powder material obtained in example 1 2 Schematic of electrode prepared by O.
Fig. 9 is a graph showing the cycle performance of the zinc ion full cells prepared in comparative example 1 and example 1.
FIG. 10 shows that the symmetric zinc ion battery assembled with the zinc-based composite powder material of comparative example 2 as a negative electrode was at 1.0mA/cm -2 And 1.0mAh/cm -2 Long cycle performance.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
The zinc powder used in the examples below in this application is commercial zinc powder purchased from the national drug group under CAS number 7440-66-6.
FIG. 1 is an apparent morphology of a sample of commercial zinc powder, and it can be seen that pure zinc powder exhibits a regular spherical appearance, a diameter of about 500nm to 2 μm, a rough appearance, and prominent spots.
Example 1
The embodiment provides a preparation method of a zinc-based composite powder material, which comprises the following steps:
immersing 5g of zinc powder into 10mL of copper sulfate solution with the concentration of 0.0516g/L, stirring for 120s at the temperature of 27 ℃ at the rotating speed of 60r/min by adopting a magnetic stirrer, taking out, taking water as a washing solvent, washing for 3 times by using a centrifuge, centrifuging at the rotating speed of 8000r/min for 3min for a single time, and drying at the temperature of 60 ℃ to obtain the Zn@Cu zinc-based composite powder material 2 O。
The embodiment also provides a method for preparing the Zn@Cu zinc-based composite powder material 2 A method for preparing a zinc ion battery with O as a negative electrode active material, comprising the steps of:
(1) Zn@Cu of zinc-based composite powder material 2 Grinding O, conductive carbon black and PVDF binder in a mass ratio of 96:2:2 in an agate mortar, adopting N-methyl pyrrolidone (NMP) as a solvent, grinding for 25min to obtain negative electrode slurry, scraping the negative electrode slurry onto a Cu foil by using a scraper with a thickness of 300nm, and drying in a vacuum oven at 60 ℃;
(2) Using a sheet punching machine to punch a Cu foil with the surface coated with electrode slurry into a wafer with the diameter of 15mm as a negative electrode, and respectively assembling a symmetrical zinc ion battery and a zinc ion full battery:
the symmetrical zinc ion battery assembly method comprises the following steps: the positive electrode and the negative electrode are both formed by assembling the 2M zinc sulfate serving as electrolyte and glass fiber serving as a diaphragm in a battery packaging machine by selecting a stainless steel battery shell, and the cycle performance of the negative electrode of the zinc ion battery is generally represented.
The zinc ion full battery is a button battery with a cathode and an anode assembled relatively, and the assembly method is as follows: 2M zinc sulfate and 0.1M manganese sulfate are used as electrolyte, glass fiber is used as a diaphragm, the anode is manganese dioxide, and a stainless steel battery shell is selected to be assembled in a battery packaging machine, so that the zinc ion battery cathode capacity retention rate is generally represented.
For the zinc-based composite powder material Zn@Cu prepared in example 1 2 The morphology of O is characterized, the results are shown in figures 2 and 3,
FIG. 2 is a Zn@Cu powder material of example 1 2 SEM image of O, from which it can be seen that after stirring for 2min in a copper sulfate solution, a large number of round particles are formed on the surface of the zinc powder and uniformly covered on the surface of the zinc powder to form a spherical frame type shell after washing and drying.
FIG. 3 is a Zn@Cu powder material of example 1 2 The TEM and HRTEM images of O can observe the shape of the small sphere on the surface of zinc powder, and the interlayer spacing between two parallel stripes is about 0.31nm in the edge region of the High Resolution Transmission Electron Microscope (HRTEM) image, corresponding to Cu 2 O (1 11 0) plane.
For the zinc-based composite powder material Zn@Cu prepared in the embodiment 2 The composition of O is characterized:
FIG. 4 is a Zn@Cu powder material of example 1 2 As can be seen from fig. 4, the XRD patterns of O show distinct diffraction peaks at 2θ≡36.3, 39.0, 43.2, 54.3, 70.1 and 70.7 °, which correspond to the (002), (100), (101), (102), (103) and (110) crystal planes of Zn (PDF # 04-0831), respectively, indicating that zinc powder main bodies are retained after the reaction. Further enlargement B shows that the XRD profile of the composite material shows new diffraction peaks at 2θ≡ 47.48, 56.68 and 63.02 ° compared to pure zinc powder, these peaks being comparable to Cu 2 The standard peak of O (PDF # 35-1091) was identical.
FIG. 5 is a Zn@Cu powder material of example 1 2 O surface high resolution XPS energy spectrum. The high resolution Cu2p spectrum shows two characteristic peaks at bond energies of 933.78 and 952.78eV, corresponding to Cu respectively 2 Cu2p of O 1/2 And Cu2p 3/2 . The results of FIGS. 4 and 5 cooperatively demonstrate Cu 2 And forming the zinc powder composite electrode material of the O-ball frame type conductive shell.
Example 2
The present embodiment providesZn@Cu containing zinc-based composite powder material prepared in example 1 2 The preparation method of the flexible negative electrode of O comprises the following steps:
Zn@Cu of zinc-based composite powder material 2 Mixing O and conductive carbon black according to the mass ratio of 10:1, adding PVDF suspension (60 wt%) and N-methylpyrrolidone (NMP) into a beaker, stirring, wherein the mass volume ratio of zinc powder to the PVDF suspension is 10g/mL, the mass volume ratio of zinc powder to N-methylpyrrolidone is 10g/mL, stirring for 30min to obtain a flexible negative electrode material (elastomer), rolling the flexible negative electrode material onto a copper mesh current collector, airing at room temperature, and cutting the obtained flexible negative electrode material into strips with the shape of rectangle and the size of 3cm multiplied by 1cm to obtain the flexible negative electrode.
The embodiment provides a preparation method of a water-based zinc ion battery with a flexible negative electrode, which comprises the following steps:
the positive electrode and the negative electrode both adopt the flexible negative electrode, the synthesized polymer hydrogel is used as electrolyte, and the high-viscosity double faced adhesive tape is used for fixing the positive electrode and the negative electrode and the gel, so that the flexible symmetric zinc ion battery is assembled.
The flexible symmetrical zinc ion battery assembled in the embodiment is 0.25mA/cm -2 ，0.25mAh/cm -2 Can be stably circulated for about 400 hours.
The preparation method of the polymer hydrogel comprises the following steps: 0.25g sodium alginate (sa) and 10ml water are evenly stirred for 4 hours, kept stand for 12 hours to remove bubbles, poured into a mould, added with 10ml 2M zinc sulfate electrolyte dropwise to polymerize the electrolyte to form gel, and finally placed in zinc sulfate solution to be soaked for 48 hours to obtain the polymer hydrogel.
Comparative example 1
Comparative example 1 used commercial zinc powder, purchased from the national drug group, CAS number 7440-66-6.
Comparative example 1 provides a method for preparing a zinc ion battery using commercial zinc powder as a negative electrode material, comprising the steps of:
(1) Grinding commercial zinc powder, conductive carbon black and PVDF binder in a mass ratio of 96:2:2 in an agate mortar, adding NMP as a solvent, grinding for 25min to obtain negative electrode slurry, scraping the negative electrode slurry onto a Cu foil by using a scraper with a thickness of 300nm, and drying in a vacuum oven at 60 ℃;
(2) A wafer with a diameter of 15mm was punched with a Cu foil coated with electrode paste on the surface as a negative electrode by using a sheet punching machine, and a symmetrical zinc ion battery and a zinc ion full battery were assembled in the same manner as in example 1, respectively.
FIG. 6 is a graph at 1.0mA/cm -2 And 1.0mAh/cm -2 Under the condition of that, the zinc-based composite powder material Zn@Cu of the embodiment 1 2 The O-assembled symmetric zinc ion cell exhibited an initial polarization voltage of only 40mV and a cycle life of 1600h, the symmetric zinc ion cell consisting of the commercial zinc powder (pure zinc powder) electrode of comparative example 1 had an initial polarization voltage of up to 254mV and a short circuit occurred only for 60h of cycling.
FIG. 7 is a graph at 10.0mA/cm -2 And a current density of 1.0mAh/cm -2 After the same time of deposition, the Zn@Cu zinc-based composite powder material of example 1 2 O and the morphology and structure of the electrode surfaces of the commercial zinc powder (pure zinc powder) of comparative example 1. After 100 cycles, the spherical structure on the commercial zinc powder electrode of comparative example 1 collapsed and was accompanied by a loose flaky structure (FIGS. 7A, B), under the same conditions, the zinc-based composite powder material Zn@Cu of example 1 2 The O-ring exhibited a spherical frame structure and remained intact (fig. 7c, d). The result proves that the Zn@Cu composite powder material 2 O can effectively inhibit zinc dendrite growth and improve zinc utilization.
FIG. 8 is a schematic diagram showing the structure of Zn@Cu powder material in example 1 2 O is prepared into a display diagram of the anode material. As can be seen from FIG. 8, the zinc-based composite powder material Zn@Cu prepared by the method 2 O can be prepared in a large scale, and the application range is widened.
The performance of the zinc ion batteries prepared in example 1 and comparative example 1 was characterized, and the results are shown in FIG. 9, from which it can be seen that the zinc-based composite powder material Zn@Cu of example 1 was used 2 The zinc ion full cell with O as the negative electrode material keeps 400 circulation capacities almost unchanged under the current density of 0.5A/g, and the zinc ion cell with commercial zinc powder as the negative electrode material has clear capacity after only 10 circulationIs significantly reduced and slowly reduced during subsequent cycles. This result demonstrates that the synthesized alloy has Cu 2 The zinc-based composite powder material of the O-ball frame type conductive shell is expected to show great application potential in the industrial production of the water-based zinc ion battery.
Comparative example 2
Comparative example 2 differs from example 1 in that zinc powder was added in an amount of 2g (below the minimum amount of the present application) and the rest of the process was identical.
The zinc-based composite powder material prepared by the comparative example is used as a negative electrode material to prepare a symmetrical zinc ion battery, performance characterization is carried out, the characterization result is shown in fig. 10, and from fig. 10, it can be seen that the symmetrical zinc ion battery assembled by taking the material as a negative electrode is 1mA/cm -2 ，1mAh/cm -2 Short circuits occur only under the condition that the circulation time is 200 hours, which is probably because when the reaction amount of zinc powder is too low, the surface structure of the zinc powder is corroded by excessive copper sulfate solution.
Comparative example 3
Comparative example 3 differs from example 1 in that zinc powder was added in an amount of 10g (higher than the highest amount of the present application) and the rest of the process was identical.
The zinc-based composite powder material prepared by the comparative example is used as a negative electrode material for preparing a symmetrical zinc ion battery, performance characterization is carried out, and test results show that the symmetrical zinc ion battery assembled by taking the material as a negative electrode is even smaller (0.5 mA/cm) -2 ，0.5mAh/cm -2 ) Short circuit occurs only for 200 hours under the conditions of current density and capacity. This is probably due to the fact that zinc powder is too high in reaction amount, so that most of zinc powder in the solution is not reacted with Cu 2+ The displacement reaction takes place to form a spherical framework.
Comparative example 4
Comparative example 4 differs from example 1 in that the copper sulfate solution concentration is different from 1.5g/L (beyond the scope of the present application), and the rest of the process is identical.
The zinc-based composite powder material prepared by the comparative example is used as a negative electrode material to prepare a symmetrical zinc ion battery, performance characterization is carried out, and test results show that the material is used as a negative electrodeElectrode assembled symmetrical zinc ion battery at 1mA/cm -2 ，1mAh/cm -2 Short-circuiting occurs only for 100 hours under the condition of (2). This may be due to the too high concentration of copper sulphate solution and the reaction process being too severe to be controlled.
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. A preparation method of a zinc-based composite powder material is characterized by comprising the following steps: zinc powder and Cu-containing alloy 2+ The aqueous solution of (C) is contacted to perform displacement reaction, solid-liquid separation is carried out, and the obtained solid is washed to remove Zn on the surface 2+ And drying to obtain the zinc-based composite powder material.
2. The method of manufacturing according to claim 1, characterized in that: the particle size of the zinc powder is 500 nm-50 mu m.
3. The method of manufacturing according to claim 1, characterized in that: the Cu-containing alloy contains 2+ Cu in aqueous solution of (C) 2+ The concentration of (2) is 0.05-1 g/L; the zinc powder and Cu-containing alloy 2+ The mass volume ratio of the aqueous solution is 0.3-0.6 g/mL.
4. The method of manufacturing according to claim 1, characterized in that: the replacement reaction is carried out under the stirring condition, the temperature of the replacement reaction is 20-30 ℃, and the time is 60-600 s.
5. The method of manufacturing according to claim 1, characterized in that: performing solid-liquid separation and washing by adopting a centrifugal separation method, wherein water is adopted as a washing solvent; the centrifugal speed is 6000-8000 r/min, the single centrifugal time is 3-10 min, and the washing times are 3-5 times; the drying temperature is 50-65 ℃ and the drying time is 6-12 h.
6. A zinc-based composite powder material produced by the production method according to any one of claims 1 to 5.
7. The zinc-based composite powder material according to claim 6, wherein: the zinc-based composite powder material is prepared by coating Cu on the surface of zinc powder 2 O-ball frame type conductive shell layer, wherein the zinc-based composite powder material is Zn@Cu 2 O。
8. Use of the zinc-based composite powder material according to claim 7 as a negative electrode active material in an aqueous zinc ion battery.
9. A method for preparing a flexible negative electrode containing the zinc-based composite powder material according to claim 7, characterized in that: the method comprises the following steps: uniformly mixing a zinc-based composite powder material, conductive carbon black, PVDF suspension and N-methylpyrrolidone to obtain a flexible anode material; and rolling the flexible anode material on a copper mesh, and drying to obtain the flexible anode.
10. An aqueous zinc ion battery employing the flexible negative electrode produced by the production method according to claim 9.
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